Electron oxidation of graphite by fluorospecies [electronic resource].
- Berkeley, Calif. : Lawrence Berkeley National Laboratory, 1984. and Oak Ridge, Tenn. : Distributed by the Office of Scientific and Technical Information, U.S. Dept. of Energy.
- Physical Description:
- Pages: 114 : digital, PDF file
- Additional Creators:
- Lawrence Berkeley National Laboratory and United States. Department of Energy. Office of Scientific and Technical Information
- The fluoride-ion affinity (A/sub F/sup -//) of phosphorus pentafluoride was determined to be 100 kcal/mole from the heats of reaction of the Lewis bases SF/sub 4/ and ClO/sub 2/F with PF/sub 5/ near room temperature. The fluoride-ion affinity of boron trifluoride was determined to be 92 kcal/mole from the heat of reaction of ClO/sub 2/F with BF/sub 3/. The crystal structure of ClO/sub 2/BF/sub 4/ was determined and a precise lattice energy was calculated from this structure and used to determined A/sub F/sup -//. Both PF/sub 5/ and BF/sub 3/ were found to react with graphite in the presence of fluorine gas to yield a variety of non-stoichiometric compounds. The fluoride-ion affinity of silicon tetrafluoride is not known, but it does not react with graphite and F/sub 2/ except at high pressures. These and previous results suggested a threshold in oxidizing power of intercalating species below which the oxidative intercalation reaction would not occur. The reduction of C/sub x/PF/sub 6/ by PF/sub 3/ proved that the reaction is thermodynamically controlled to some extent. The displacement of PF/sub 5/ in C/sub x/PF/sub 6/ by BF/sub 3/ (with a smaller A/sub F/sup -//) suggested that two BF/sub 3/ molecules may have a larger fluoride-ion affinity than one PF/sub 5/ and that B/sub 2/F/sub 7//sup -/ may be a stable anion in graphite. Conductivity studies of PF/sub x/ and BF/sub y/ salts showed that a large drop in conductivity when the reaction reaches first stage is due in the most part to direct fluorination of carbon in graphite.
- Published through SciTech Connect., 09/01/1984., "lbl-18367", "DE85001196", and Rosenthal, G.L.
- Funding Information:
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